The reaction pathway for the tandem aza-Cope rearrangement - Mannich cyclization reaction leading to substituted acyl pyrrolidines is mapped using density functional methods. Activation barriers and relative energies of intermediates are calculated at the B3LYP/cc-pVQZ level of theory for a series of pyrrolidines with a range of substituents. Using boron trifluoride as the acid catalyst, we examine the effects of varying the size and electronic characteristics of the protecting group and of substituents at two positions on the pyrrolidine ring on the activation energies and relative stability of intermediates.

Substituent effects in a Lewis acid catalyzed aza-Cope Mannich tandem reaction

244th National Meeting (2012)

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